CN109119713A - A kind of method of positive active material in recycling lithium ion battery - Google Patents
A kind of method of positive active material in recycling lithium ion battery Download PDFInfo
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- CN109119713A CN109119713A CN201810970695.4A CN201810970695A CN109119713A CN 109119713 A CN109119713 A CN 109119713A CN 201810970695 A CN201810970695 A CN 201810970695A CN 109119713 A CN109119713 A CN 109119713A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a kind of methods of positive active material in recycling lithium ion battery.This method first crushes the positive plate of refuse battery, and screening obtains aluminium foil particle and black powder；Resulting mixed slurry is reacted to black powder and polar solvent and is filtered separation；Specifically: it takes part mixed slurry to be sent into filter plant and is filtered for the first time, stop filtering when the thickness of filter cake reaches 1-10cm, obtain filter cake and filtrate A；The filter cake places certain time to its film forming agglomeration, then one layer of filter cloth, that is, second layer filter cloth is placed on it, remaining mixed slurry and filtrate A are filtered on second layer filter cloth later, collecting the filter residue on second layer filter cloth is the positive active material recycled and the mixture of conductive carbon black；The polar solvent that filtering gained liquor B is recycled after flocculation sedimentation, distillation.The method of the invention solves the problems, such as the filtration difficulty occurred in existing solvent method separation positive active material and adhesive process.
Description
Technical field
The present invention relates to the recovery processings of lithium ion battery, and in particular to positive electrode active material in a kind of recycling lithium ion battery
The method of matter.
Background technique
With the demand of global lithium ion battery and being continuously increased for yield, the quantity of waste and old lithium ion battery is also anxious therewith
Speed increases.Containing noxious materials such as various heavy, organic and inorganic compounds in waste and old lithium ion battery, in the environment easily
Various chemical reactions occur, easily cause environmental pollution, some of compounds have more carcinogenicity, endanger human health；Certain
A little solvents are readily burned, and easily cause fire；On the other hand, usually contained in the positive electrode in waste and old lithium ion battery lithium,
The valuable metals element such as cobalt, nickel and manganese, wherein cobalt and nickel are most economical in waste and old lithium ion battery as a kind of strategy metal
The metallic element of benefit.Therefore, waste and old lithium ion battery is recycled with great economic benefit, it may have important
Environmental protection and social benefit.
Currently, the substance mainly recycled in waste and old lithium ion battery is copper, aluminium, positive electrode and negative electrode material, wherein lithium
Battery anode slice is that aluminium foil applies positive electrode, and lithium battery cathode plate is that copper foil applies negative electrode material.Comprehensive research both domestic and external
Status, usually contain three key steps in recycling: first, old and useless battery discharge treatment early period and dismantling；Second, electrode
The separation of material and collector；Third, the recycling and utilization of valuable metal.The positive electrode of lithium ion battery is mainly living by anode
Property substance (such as nickle cobalt lithium manganate or LiFePO4), conductive black and bonding agent composition, three is mixed and made into anode sizing agent, then
Anode sizing agent is coated on aluminium foil, positive plate is obtained after drying.Since positive active material, conductive black and binder are logical
It crosses binder close adhesion and is adhered on aluminium foil, the prior art by positive active material, conductive black and is glued frequently with solvent
Knot agent three is scattered in solvent (wherein binder can be dissolved in solvent, and positive active material and conductive black are then insoluble),
Further realize positive active material and binder separation.But the liquid formed after being dissolved by the solvent due to binder is very
It is sticky, and positive active material is the lesser attritive powder of granularity, is being carried out using existing conventional filter type to them
When separation, not only the rate of filtration is slow, but also still contains a large amount of positive active materials after filtering in resulting filtrate, therefore limit
The application of solvent separation this method of aluminium foil and positive electrode.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods of positive active material in recycling lithium ion battery, should
Method efficiently solves the problems, such as the filtration difficulty occurred in existing solvent method separation positive active material and adhesive process, moreover it is possible to
Make the polar solvent recycling for dissolving binder.
In order to solve the above technical problems, the method for the present invention for recycling positive active material in lithium ion battery, packet
Include following steps:
(1) it is disassembled after waste and old lithium ion battery discharging, collects positive plate；
(2) positive plate is crushed, sieves, respectively obtains aluminium foil particle and black powder；
(3) black powder and polar solvent are uniformly mixed, are reacted under the conditions of being heated or not heated, after the reaction was completed
To mixed slurry；Wherein, the polar solvent is selected from N-Methyl pyrrolidone, trifluoroacetic acid, ethyl alcohol, acetone, salicylic acid
The combination of one or more of methyl esters, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide；
(4) it takes part mixed slurry to be sent into filter plant to be filtered for the first time, stop when the thickness of filter cake reaches 1-10cm
It only filters, collects filtrate, be denoted as filtrate A；The filter cake that first filtering is formed is placed into certain time to its film forming agglomeration, is then existed
One layer of filter cloth, that is, second layer filter cloth is placed thereon, and remaining mixed slurry and filtrate A are sent into filter plant second later
Layer filter cloth on be filtered, filtering inventory close to filter plant design treatment amount when collect second layer filter cloth on filter
Slag repeats carry out the filtering of remaining mixed slurry on second layer filter cloth later, collects the filter residue operation on second layer filter cloth,
Until mixed slurry has all filtered, filtrate is collected, liquor B is denoted as, and the filter residue on the second layer filter cloth of aforementioned collection is
The positive active material of recycling and the mixture of conductive black；
(5) liquor B be sent directly into or return step (3) in replace polar solvent be recycled at least 1 time after be sent into precipitating
Slot is added flocculant and carries out flocculation sedimentation, be separated by solid-liquid separation later, collects filtrate, be denoted as liquor C；Filter residue is collected, it is as viscous
Tie the mixture of agent and flocculant；
(6) liquor C is distilled, collects distillate or kettle raffinate, the polar solvent as recycled.
In above-mentioned steps (1), waste and old lithium ion battery is discharged and disassembled using existing conventional techniques, is then collected
Positive plate.The waste and old lithium ion battery can be the waste and old lithium ion battery that positive active material is LiFePO4, or
It is the waste and old lithium ion battery that positive active material is ternary material (containing lithium, nickel, cobalt, manganese or aluminium).
In above-mentioned steps (2), when being sieved to smashed positive plate, it is preferred to use 100-300 mesh even mesh number
Smaller sieve.
In order to further realize the recycling to aluminium foil, the method for the invention can also further comprise carrying out to aluminium foil particle
The step of recycling (3a), specifically:
Aluminium foil particle and polar solvent are uniformly mixed by (3a), are reacted under the conditions of being heated or not heated, after the reaction was completed
Gained reactant material is separated by solid-liquid separation, filter residue, the aluminium foil as recycled are collected；Filtrate is collected, filtrate D is denoted as；Wherein, institute
The polar solvent stated is selected from N-Methyl pyrrolidone, trifluoroacetic acid, ethyl alcohol, acetone, gaultherolin, N, N- dimethyl formyl
The combination of one or more of amine and DMAC N,N' dimethyl acetamide.
The step (3) and step (3a) can be carried out sequentially in no particular order, can also be carried out simultaneously.In step (3),
The consumption proportion of the polar solvent and black powder is 1-50L:1kg, and in step (3a), the use of the polar solvent
Amount is usually 1-4 times of aluminium foil particle volume.
For filtrate D obtained in step (3a), subsequent processing identical with filtrate A in step (4) can be carried out, i.e., will
Filtrate D is sent into filter plant and is filtered on second layer filter cloth, collects filtrate and carries out the behaviour of flocculation sedimentation described in step (5)
Make, collecting filter residue is the positive active material recycled and the mixture of conductive carbon black.
In above-mentioned steps (3) or step (3a), the reaction is usually carried out under the conditions of≤100 DEG C as specifically can be
It carries out under the conditions of 10-100 DEG C, is preferably carried out under the conditions of 30-90 DEG C.Time of reaction usually >=0.1h, wherein in step (3)
Reaction time be more preferably 1-10h, and the reaction time in step (3a) is more preferably 1-7h.
In above-mentioned steps (4), the filter plant is conventional selection in the prior art, usually plate and frame filter press.
Filter cloth used in filter plant is usually fiber filter cloth, is not required particularly the aperture of filter cloth, preferably 150-400
Mesh.In first filtering, preferably stop filtering when the thickness of filter cake is in 3-6cm.Collect the filter cake that filtrate filters formation for the first time
Usually it can make its film forming agglomeration in placement 1-6h.The present invention first filters part mixed slurry, and the filter cake of formation is tied in film forming
It is used as filter medium together with the second layer filter cloth on the first layer filter cloth of its bottom and its surface after block, so that water in mixed slurry
Property liquid (binder is dissolved completely in the solution formed in polar solvent) can pass through filter cloth and filter cake void, and will be micro-
The positive active material and carbon black of small particle are retained down, and realize that the time being separated by filtration is of short duration, therefore, using such mistake
Filter medium and filter type effectively improve the strainability of mixed slurry, solve existing solvent method separation positive active material
With the filtration difficulty problem occurred in adhesive process.
In above-mentioned steps (5), the flocculant is conventional selection in the prior art, specifically be can be selected from chlorination
The combination of one or more of iron, aluminium polychloride, aluminium chloride, aluminum sulfate and ferric sulfate.For the dosage of flocculant,
The usually 1-40% of solution quality.It after flocculant is added, stands after first stirring a period of time, is had in precipitating trench bottom again
The substance united generates, after supernatant liquid it is limpid it is bright after material can be separated by solid-liquid separation and (usually be filtered).General feelings
Under condition, it is 5-300min that the time stirred after flocculant, which is added, and the time of standing is 10-600min.
In above-mentioned steps (6), distillation procedure carries out usually in distillation still, and the pressure and temperature of distillation still can specifically be set
Be set to 5-101.3kpa, 10-140 DEG C, collect distillate or kettle raffinate, the polar solvent as recycled, can return to step (3) and
Step (3a) uses, and another liquid distilled is water.
Compared with prior art, present invention is characterized in that
1, the method for the invention realizes positive active material in lithium ion battery (practical is positive active material and lead
Electric black stock) and binder between separation, specifically first part mixed slurry is filtered, the filter cake of formation is tied in film forming
It is used as filter medium together with the second layer filter cloth on the first layer filter cloth of its bottom and its surface after block, so that water in mixed slurry
Property liquid (binder is dissolved completely in the solution formed in polar solvent) can pass through filter cloth and filter cake void, and will be micro-
The positive active material and carbon black of small particle are retained down, and realize that the time being separated by filtration is of short duration, therefore, using such mistake
Filter medium and filter type effectively improve the strainability of mixed slurry, solve existing solvent method separation positive active material
With the filtration difficulty problem occurred in adhesive process.The mixture for recycling resulting positive active material and conductive black enters
Subsequent handling extracts valuable element therein, and the mixture of resulting binder and flocculant then can as needed it is outer sell or into
Row landfill.
2, the method for the invention realizes the recycling of polar solvent, reduces production cost.Solvent passes through flocculation
Two steps of precipitating and distillation are recycled, and are reduced the energy consumption of solvent recovery process, be further reduced production cost.
4 further, realizes the recycling to aluminium foil, and the aluminium foil of recycling can be used for regenerating the preparation of aluminium or aluminium foil, from
And it is re-used for the production of lithium ion battery.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, content to better understand the invention, but
The present invention is not limited to following embodiments.
Embodiment 1
(1) waste and old cobalt acid lithium battery is disassembled after conventional discharge, dry, is first removed shell, take out battery core,
Diaphragm, positive plate and the negative electrode tab in battery core are separated again, collect positive plate；
Positive plate feeding pulverizer is crushed as fragment, screening machine of the resulting material feeding screen mesh size for 200 mesh, difference
Obtain aluminium foil particle and black powder；
(3) black powder is placed in the first stirred tank, polar solvent (N-Methyl pyrrolidone) is added thereto, polarity
The liquid-solid ratio of solvent and black powder is 10L:1kg, is warming up to 50 DEG C and is stirred to react 6h, obtains mixed slurry；
Aluminium foil particle is placed in the second stirred tank by (3a), polar solvent (N-Methyl pyrrolidone) is added thereto, pole
Property solvent additional amount be 2 times of aluminium foil particle volume, be warming up to 50 DEG C and be stirred to react 2h, obtained reactant is filtered
(aperture of filter screen is 200 mesh), collects filter residue and filtrate, wherein filter residue is the aluminium foil of recycling, for regenerating aluminium or regeneration respectively
The preparation of aluminium foil still contains a small amount of solid in filtrate；
(4) mixed slurry (filter cloth aperture is 150 mesh) is sent into filter plant (plate and frame filter press) to be filtered for the first time,
Stop filtering when the thickness of filter cake is in 4cm, collects filtrate, be denoted as filtrate A；The filter cake that first filtering is formed is placed into 6h, institute
It states that filter cake surface has formed a film and entire filter cake has agglomerated drying, one layer of filter cloth i.e. second is then placed on the surface of the filter cake
Layer filter cloth (filter cloth aperture is 150 mesh), the filtrate for later collecting remaining mixed slurry, filtrate A and step (3a) is sent into
Filter plant is filtered on second layer filter cloth, and residence time of the material on second layer filter cloth is less than 1min, collects filtrate,
It is denoted as liquor B, collecting the filter residue on second layer filter cloth is the positive active material recycled and the mixture of conductive black；
(5) precipitation tank is sent into after replacing polar solvent to be recycled 100 times in liquor B return step (3), concentration, which is added, is
The ferric chloride solution of 5g/L, ferric chloride solution additional amount are the 20% of solvent quality, stir 20min, stand 60min, filter, receive
Collect filtrate, is denoted as liquor C；Collect filter residue, the as mixture of binder and flocculant；
(6) liquor C feeding distillation still is distilled, pressure when distillation is 80kpa, temperature is 70 DEG C, and collection distillates
Liquid, the N-Methyl pyrrolidone as recycled can return in step (3) or step (3a) and use, another liquid distilled
Body is water, is recycled in process of production.
Elemental analysis and gravimetric analysis are carried out to the resulting mixture of the present embodiment step (4).Gravimetric analysis the result shows that,
The quality of mixture obtained by step (4) accounts for 99.1% of black powder quality obtained by step (2).Elemental analysis the result shows that, step
Suddenly containing lithium, cobalt, four kinds of oxygen, carbon elements in mixture obtained by (4), mass percent is respectively 7.1%, 60.2%,
30.45%, 2.25%, therefore mixture is the mixture of cobalt acid lithium and carbon black.
Elemental analysis is carried out to the resulting mixture of the present embodiment step (5), contains four kinds of iron, chlorine, carbon, fluorine elements, matter
Measuring percentage is respectively 20.8%, 39.2%, 16.4%, 23.6%, therefore mixture is iron chloride and the mixture of PVDF.
Embodiment 2
Embodiment 1 is repeated, unlike:
In step (1), old and useless battery is waste lithium manganese oxide battery；
In step (3), polar solvent is acetone, and the liquid-solid ratio of polar solvent and black powder is 40L:1kg, is reacted 40
It is carried out under the conditions of DEG C, reaction time 2h；
It omits step (3a)；
Step (4) are as follows: mixed slurry is sent into filter plant (plate and frame filter press) (filter cloth aperture is 200 mesh) and is carried out just
Secondary filtering stops filtering when the thickness of filter cake reaches 6cm, collects filtrate, is denoted as filtrate A；The filter cake that first filtering is formed
4h is placed, then drying that the filter cake surface has formed a film and entire filter cake has agglomerated places one layer on the surface of the filter cake
Filter cloth, that is, second layer filter cloth (filter cloth aperture is 150 mesh), send remaining mixed slurry and filtrate A into filter plant later and exists
It being filtered on second layer filter cloth, residence time of the material on second layer filter cloth is less than 1min, and filtrate is collected, liquor B is denoted as,
Collecting the filter residue on second layer filter cloth is the positive active material recycled and the mixture of conductive black；
In step (5), it is sent into precipitation tank after replacing polar solvent to be recycled 100 times in liquor B return step (3), is added
Enter the polyaluminum chloride aqueous solution that concentration is 15g/L, additional amount is the 10% of solvent quality, stirs 100min, stands 300min；
In step (6), pressure when distillation is 101.3kpa, and temperature is 40 DEG C.
Elemental analysis and gravimetric analysis are carried out to the resulting mixture of the present embodiment step (4).Gravimetric analysis the result shows that,
The quality of mixture obtained by step (4) accounts for 99.5% of black powder quality obtained by step (2).Elemental analysis the result shows that, step
Suddenly mixture obtained by (4) contains four kinds of lithium, manganese, oxygen, carbon elements, and mass percent is respectively 7.2%, 61.1%, 29%,
2.8%, therefore mixture is the mixture of LiMn2O4 and carbon black.
The present embodiment step (5) resulting mixture is collected, elemental analysis is carried out, containing four kinds of aluminium, chlorine, carbon, fluorine elements,
Mass percent is respectively 10.2%, 39.9%, 20.4%, 29.5%, therefore mixture is aluminium chloride and the mixture of PVDF.
Embodiment 3
Embodiment 1 is repeated, unlike:
In step (1), old and useless battery is waste and old nickle cobalt lithium manganate battery；In step (3), polar solvent is trifluoroacetic acid,
The liquid-solid ratio of polar solvent and black powder is 5L:1kg, and reaction carries out under the conditions of 40 DEG C, reaction time 2h；
In step (3a), polar solvent is trifluoroacetic acid, and the additional amount of polar solvent is 4 times of aluminium foil particle volume, instead
It should be carried out under the conditions of 30 DEG C, reaction time 1h；Gained reactant aperture of strainer used in filtering is 100 mesh, filtering
The still a small amount of solid of content in resulting filtrate；
Step (4) are as follows: mixed slurry is sent into filter plant (plate and frame filter press) (filter cloth aperture is 250 mesh) and is carried out just
Secondary filtering stops filtering when the thickness of filter cake is in 8cm, collects filtrate, is denoted as filtrate A；The filter cake that first filtering is formed is put
3h is set, then one layer of filter is placed in drying that the filter cake surface has formed a film and entire filter cake has agglomerated on the surface of the filter cake
Cloth, that is, second layer filter cloth (filter cloth aperture is 200 mesh), will collect in remaining mixed slurry, filtrate A and step (3a) later
Filtrate be sent into filter plant together and be filtered on second layer filter cloth, residence time of the material on second layer filter cloth is less than
1min collects filtrate, is denoted as liquor B, and collecting the filter residue on second layer filter cloth is the positive active material recycled and conductive charcoal
Black mixture；
In step (5), the ferric sulfate aqueous solution that concentration is 8g/L is added, additional amount is the 15% of solvent quality, stirring
10min stands 30min；
In step (6), pressure when distillation is 90kpa, and temperature is 50 DEG C.
Elemental analysis and gravimetric analysis are carried out to the resulting mixture of the present embodiment step (4).Gravimetric analysis the result shows that,
The quality of mixture obtained by step (4) accounts for 99.7% of black powder quality obtained by step (2).Elemental analysis the result shows that, step
Suddenly mixture obtained by (4) contains six kinds of lithium, nickel, cobalt, manganese, oxygen, carbon elements, and mass percent is respectively 7.05%, 20.1%,
20.2%, 18.1%, 31%, 3%, therefore mixture is the mixture of nickle cobalt lithium manganate and carbon black.
To the present embodiment step (5) resulting mixture, elemental analysis is carried out, five kinds of iron, sulphur, oxygen, carbon, fluorine members are contained
Element, mass percent are respectively 18.2%, 11.4%, 35.2%, 14.3%, 20.9%, thus mixture be ferric sulfate and
The mixture of PVDF.
Embodiment 4
Embodiment 1 is repeated, unlike:
In step (1), old and useless battery is waste lithium iron phosphate battery；
In step (3), polar solvent is n,N-Dimethylformamide, and the liquid-solid ratio of polar solvent and black powder is 35L:
1kg, reaction carry out under the conditions of 70 DEG C, reaction time 5h；
It omits step (3a)；
Step (4) are as follows: mixed slurry is sent into filter plant (plate and frame filter press) (filter cloth aperture is 300 mesh) and is carried out just
Secondary filtering stops filtering when the thickness of filter cake is in 2cm, collects filtrate, is denoted as filtrate A；The filter cake that first filtering is formed is put
1h is set, then one layer of filter is placed in drying that the filter cake surface has formed a film and entire filter cake has agglomerated on the surface of the filter cake
Remaining mixed slurry and filtrate A are sent into filter plant the later by cloth, that is, second layer filter cloth (filter cloth aperture be 200 mesh)
It is filtered on two layers of filter cloth, residence time of the material on second layer filter cloth is less than 1min, collects filtrate, is denoted as liquor B, receives
Collecting the filter residue on second layer filter cloth is the positive active material recycled and the mixture of conductive black；
In step (5), it is sent into precipitation tank after replacing polar solvent to be recycled 70 times in liquor B return step (3), is added
Concentration is the ferric sulfate aqueous solution of 5g/L, and additional amount is the 25% of solvent quality, stirs 20min, stands 90min；
In step (6), pressure when distillation is 60kpa, and temperature is 120 DEG C, collects kettle raffinate, the N as recycled, N- bis-
Methylformamide can return in step (3) and use, and another liquid distilled is water, be recycled in process of production.
Elemental analysis and gravimetric analysis are carried out to the resulting mixture of the present embodiment step (4).Gravimetric analysis the result shows that,
The quality of mixture obtained by step (4) accounts for 99.4% of black powder quality obtained by step (2).Elemental analysis the result shows that, step
Suddenly mixture obtained by (4) contains lithium, iron, phosphorus, oxygen, four or five element of carbon, and mass percent is respectively 4.05%, 34.8%, 18%,
41%, 2.1%, therefore mixture is the mixture of LiFePO4 and carbon black.
To the present embodiment step (5) resulting mixture, elemental analysis is carried out, five kinds of iron, sulphur, oxygen, carbon, fluorine members are contained
Element, mass percent are respectively 18.2%, 11.4%, 35.2%, 14.3%, 20.9%, thus mixture be ferric sulfate and
The mixture of PVDF.
Embodiment 5
Embodiment 1 is repeated, unlike:
In step (1), old and useless battery is waste and old nickle cobalt lithium manganate battery；
In step (3), polar solvent is n,N-dimethylacetamide, and the liquid-solid ratio of polar solvent and black powder is 15L:
1kg, reaction carry out under the conditions of 80 DEG C, reaction time 2.5h；
It omits step (3a)；
Step (4) are as follows: mixed slurry is sent into filter plant (plate and frame filter press) (filter cloth aperture is 150 mesh) and is carried out just
Secondary filtering stops filtering when the thickness of filter cake is in 9cm, collects filtrate, is denoted as filtrate A；The filter cake that first filtering is formed is put
2h is set, then one layer of filter is placed in drying that the filter cake surface has formed a film and entire filter cake has agglomerated on the surface of the filter cake
Remaining mixed slurry and filtrate A are sent into filter plant the later by cloth, that is, second layer filter cloth (filter cloth aperture be 150 mesh)
It is filtered on two layers of filter cloth, residence time of the material on second layer filter cloth is less than 1min, collects filtrate, is denoted as liquor B, receives
Collecting the filter residue on second layer filter cloth is the positive active material recycled and the mixture of conductive black；
In step (5), it is sent into precipitation tank after replacing polar solvent to be recycled 70 times in liquor B return step (3), is added
Concentration is the polyaluminum sulfate aluminum water solution of 20g/L, and additional amount is the 12% of solvent quality, stirs 15min, stands 150min；
In step (6), pressure when distillation is 70kpa, and temperature is 130 DEG C, collects kettle raffinate, the N as recycled, N- bis-
Methylacetamide can return in step (3) and use, and another liquid distilled is water, be recycled in process of production.
Elemental analysis and gravimetric analysis are carried out to the resulting mixture of the present embodiment step (4).Gravimetric analysis the result shows that,
The quality of mixture obtained by step (4) accounts for 99.8% of black powder quality obtained by step (2).Elemental analysis the result shows that, step
Suddenly mixture obtained by (4) contains six kinds of lithium, nickel, cobalt, manganese, oxygen, carbon elements, and mass percent is respectively 6.9%, 20.8%,
19.1%, 18.8%, 30.6%, 2.99%, therefore mixture is the mixture of nickle cobalt lithium manganate and carbon black.
Elemental analysis is carried out to the resulting mixture of the present embodiment step (5), containing five kinds of aluminium, sulphur, oxygen, carbon, fluorine elements,
Mass percent is respectively 9.62%, 16.8%, 33.2%, 16.5%, 23.9%, therefore mixture is aluminum sulfate and PVDF
Mixture.
Claims (9)
1. a kind of method of positive active material in recycling lithium ion battery, comprising the following steps:
(1) it is disassembled after waste and old lithium ion battery discharging, collects positive plate；
(2) positive plate is crushed, sieves, respectively obtains aluminium foil particle and black powder；
(3) black powder and polar solvent are uniformly mixed, are reacted under the conditions of being heated or not heated, mixed after the reaction was completed
Close slurry；Wherein, the polar solvent be selected from N-Methyl pyrrolidone, trifluoroacetic acid, ethyl alcohol, acetone, gaultherolin,
The combination of one or more of N,N-dimethylformamide and DMAC N,N' dimethyl acetamide；
(4) it takes part mixed slurry to be sent into filter plant to be filtered for the first time, stop when the thickness of filter cake reaches 1-10cm
Filter collects filtrate, is denoted as filtrate A；By the filter cake placement certain time of first filtering formation to its film forming agglomeration, then on it
One layer of filter cloth i.e. second layer filter cloth is placed, remaining mixed slurry and filtrate A are sent into filter plant later and filtered in the second layer
It is filtered on cloth, the filter residue on second layer filter cloth is collected when design treatment amount of the inventory of filtering close to filter plant,
It repeats later and carries out the filtering of remaining mixed slurry on second layer filter cloth, collect the filter residue operation on second layer filter cloth, directly
It has all been filtered to mixed slurry, has collected filtrate, be denoted as liquor B, and the filter residue on the second layer filter cloth of aforementioned collection is back
The positive active material of receipts and the mixture of conductive black；
(5) liquor B is sent directly into or return step (3) is middle instead of being sent into precipitation tank after polar solvent recycling at least 1 time, is added
Enter flocculant and carry out flocculation sedimentation, be separated by solid-liquid separation later, collects filtrate, be denoted as liquor C；Collect filter residue, as binder
With the mixture of flocculant；
(6) liquor C is distilled, collects distillate or kettle raffinate, the polar solvent as recycled.
2. according to the method described in claim 1, it is characterized by also including (3a) the step of recycling to aluminium foil particle,
Specifically:
Aluminium foil particle and polar solvent are uniformly mixed by (3a), are reacted under the conditions of being heated or not heated, after the reaction was completed to institute
It obtains reaction mass to be separated by solid-liquid separation, collects filter residue, the aluminium foil as recycled；Filtrate is collected, filtrate D is denoted as；Wherein, described
Polar solvent be selected from N-Methyl pyrrolidone, trifluoroacetic acid, ethyl alcohol, acetone, gaultherolin, N,N-dimethylformamide and
The combination of one or more of DMAC N,N' dimethyl acetamide.
3. according to the method described in claim 2, it is characterized by: filtrate D is carried out subsequent processing identical with filtrate A.
4. according to the method described in claim 2, it is characterized by: the dosage of the polar solvent is the 1- of aluminium foil particle volume
4 times.
5. method according to any of claims 1-4, it is characterised in that: in step (3) or step (3a), reaction exists
It is carried out under the conditions of≤100 DEG C.
6. method according to any of claims 1-4, it is characterised in that: in step (3) or step (3a), reaction
Time >=0.1h.
7. method according to any of claims 1-4, it is characterised in that: in step (3) or step (3a), reaction
Time is 1-10h.
8. method according to any of claims 1-4, it is characterised in that: in step (3), the polar solvent with
The consumption proportion of black powder is 1-50L:1kg.
9. method according to any of claims 1-4, it is characterised in that: in step (5), the flocculant is choosing
From the combination of one or more of iron chloride, aluminium polychloride, aluminium chloride, aluminum sulfate and ferric sulfate.
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| CN113173875A (en) * | 2021-05-12 | 2021-07-27 | 南京长江江宇环保科技有限公司 | Method for recycling N-methyl pyrrolidone from waste anode electrode slurry in lithium battery production |
| CN113690502A (en) * | 2021-07-23 | 2021-11-23 | 广东邦普循环科技有限公司 | Method for recycling waste battery slurry |
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| CN113690502B (en) * | 2021-07-23 | 2024-03-08 | 广东邦普循环科技有限公司 | Method for recycling waste battery slurry |
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